Radiation-curable, cyanoacrylate-containing compositions

ABSTRACT

A radiation-curable composition which includes a cyanoacrylate component or a cyanoacrylate-containing formulation; a metallocene component; and a polymerizingly effective amount of a photoinitiator to accelerate the rate of cure is provided.

RELATED APPLICATION DATA

This application is a continuation of U.S. patent application Ser. No.09,486,423, filed Oct. 20, 1999 (now U.S. Pat. No. 6,433,036, issuedAug. 13, 2002), which is the U.S. National phase entry of InternationalPatent Application No. PCT/US98/03819, filed Feb. 26, 1998, which is acontinuation-in-part of U.S. patent application Ser. No. 08/805,193,filed Feb. 27, 1997 (now U.S. Pat. No. 5,922,783, issued Jul. 13, 1999).

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a radiation-curable composition whichincludes a cyanoacrylate component or a cyanoacrylate-containingformulation, a metallocene component and a polymerizingly effectiveamount of a photoinitiator to accelerate the rate of cure.

2. Brief Description of Related Technology

Cyancacrylates generally are quick-setting materials which cure toclear, hard glassy resins, useful as sealants, coatings, andparticularly adhesives for bonding together a variety of substrates [seee.g., H. V. Coover, D. W. Dreifus and J. T. O'Conner, “CyanoacrylateAdhesives” in Handbook of Adhesives, 27, 463-77, I. Skeist, ed., VanNostrand Reinhold, N.Y., 3rd ed. (1990)].

Ordinarily, upon contact with substrate materials possessing a surfacenucleophile, cyanoacrylate-containing compositions spontaneouslypolymerize to form a cured material. The cured material exhibitsexcellent adhesive properties to materials such as metals, plastics,elastomers, fabrics, woods, ceramics and the like.Cyanoacrylate-containing compositions are thus seen as a versatile classof single-component, ambient temperature curing adhesives.

As noted, cyanoacrylate polymerization is typically initiated using anucleophile. The cyanoacrylate anionic polymerization reaction proceedsuntil all available cyanoacrylate monomer has been consumed and/orterminated by an acidic species.

Although the predominant mechanism by which cyanoacrylate monomersundergo polymerization is an anionic one, free-radical polymerization isalso known to occur in this regard under prolonged exposure to heat orlight of an appropriate wavelength. See e.g., Coover et al., supra.Ordinarily, however, free-radical stabilizers, such as quinones orhindered phenols, are included in cyanoacrylate-containing adhesiveformulations to extend their shelf life. Thus, the extent of anyfree-radical polymerization of commercial cyanoacrylate-containingcompositions is typically minimal and in fact is especially undesirablefor at least the reason stated.

With conventional polymerizable compositions other than those containingcyanoacrylate monomers, radiation cure generally presents certainadvantages over other known cure methods. Those advantages includereduced cure time, solvent elimination (which thereby reducesenvironmental pollution, and conserves raw materials and energy) andinducement of low thermal stressing of substrate material. Also, roomtemperature radiation cure prevents degradation of certain heatsensitive polymers, which may occur during a thermal cure procedure.

Radiation-curable, resin-based compositions are legion for a variety ofuses in diverse industries, such as coatings, printing, electronic,medical and general engineering. Commonly, radiation-curablecompositions are used for adhesives, and in such use the resin mayordinarily be chosen from epoxy- or acrylate-based resins.

Well-known examples of radiation-curable, epoxy-based resins includecycloaliphatic and bisphenol-A epoxy resins, epoxidized novolacs andglycidyl polyethers. [See e.g., U.S. Pat. No. 4,690,957 (Fujiokau) andEuropean Patent Publication EP 278 685.] The common cure mechanism forsuch radiation-curable epoxy-based compositions is reported to becationic polymerization.

Well-known examples of radiation-curable, acrylate-based resins includethose having structural backbones of urethanes, amides, imides, ethers,hydrocarbons, esters and siloxanes. [See e.g., J. G. Woods,“Radiation-Curable Adhesives” in Radiation Curing: Science andTechnology, 333-98, 371, S. P. Pappas, ed., Plenum Press, New York(1992).] The common cure mechanism for such radiation-curable,acrylate-based compositions is free-radical polymerization.

European Patent Publication EP 393 407 describes a radiation-curablecomposition which includes a slow cure cationic polymerizable epoxide, afast cure free radical polymerizable acrylic component and aphotoinitiator. Upon exposure to radiation, the photoinitiator is saidto be capable of generating a cationic species which is capable ofinitiating polymerization of the epoxide and a free radical specieswhich is capable of initiating polymerization of the acrylic component.The polymerizable acrylic component includes monofunctional acrylatesand acrylate esters, such as cyano-functionalized acrylates and acrylateesters, examples of which are expressed as 2-cyanoethyl acrylate(CH₂═CHCOOCH₂CH₂CN) and 3-cyanopropyl acrylate (CH₂═CHCOOCH₂CH₂CH₂CN).(See page 5, lines 19-26.) The photoinitiator includes onium salts ofGroup Va, VIa and VIIa as well as iron-arene complexes, and generallymetallocene salts, provided that the material chosen as thephotoinitiator is said to be one which is capable of generating both acationic species and a free radical species upon exposure to radiation.(See page 5, line 56-page 7, line 15.)

Other reported information regarding photopolymerizable compositionsincludes formulations containing epoxy compounds and metal complexes,such as disclosed in U.S. Pat. No. 5,525,698 (Böttcher).

U.S. Pat. No. 4,707,432 (Gatechair) speaks to a free radicalpolymerizable composition which includes (a) polymerizable partialesters of epoxy resins and acrylic and/or methacrylic, and partialesters of polyols and acrylic acid and/or methacrylic acid, and (b) aphotoinitiator blend of a cyclopentadienyl iron complex and a sensitizeror photoinitiator, such as an acetophenone.

In D. B. Yang and C. Kutal, “Inorganic and organometallicPhotoinitiators” in Radiation Curing. Science and Technology, 21-55, S.P. Pappas, ed., Plenum Press, New York (1992), cyclopentadienyltransition metal complexes are discussed with attention paid toferrocene and titanocene. In the absence of halogenated media, Yang andKutal report that ferrocene is photoinert, though in the presence ofsuch media and a vinyllic source free radical initiated polymerizationmay occur.

And in C. Kutal, P. A. Grutsch and D. B. Yang, “A Novel Strategy forPhotoinitiated Anionic Polymerization”, Macromolecules, 24, 6872-73(1991), the authors note that “[c]onspicuously absent from the currentcatalogue of photoinitiators are those that undergo photochemicalrelease of an anionic initiating species.” The authors also note thatethyl cyanoacrylate is “unaffected by prolonged (24-h) irradiation withlight of wavelength >350 nm” whereas in the presence of NCS⁺,cyanoacrylate is observed to solidify immediately, generating heat inthe process. Though the NCS⁻ was not in that case generated as a resultof irradiation, it was generated from the Reineckate anion upon ligandfield excitation thereof with near-ultraviolet/visible light.

While metallocenes (such as ferrocenes) have been employed inacrylate-based anaerobic adhesive compositions [see e.g., U.S. Pat. No.3,855,040 (Malofsky), U.S. Pat. No. 4,525,232 (Rooney), U.S. Pat. No.4,533,446 (Conway) and EP '407], it is not believed that to date acyanoacrylate-based adhesive composition has been developed includingtherein a metallocene as defined herein, particularly with respect tocuring through a photoinitiated mechanism.

Accordingly, a photocurable composition including a cyanoacrylatecomponent, a metallocene component and a photoinitiator component wouldbe desirable as possessing the benefits and advantages ofcyanoacrylate-containing compositions while curing through at least aphoto-induced polymerization mechanism.

SUMMARY OF THE INVENTION

The present invention meets the desire expressed above by providingcompositions which include a cyanoacrylate component or acyanoacrylate-containing formulation, a metallocene component and aphotoinitiator. Desirably, such compositions are curable after exposureto radiation in the electromagnetic spectrum. Accordingly, in suchradiation or photocurable compositions a polymerizingly effective amountof a photoinitiator should be used.

The photocurable compositions of this invention retain those benefitsand advantages of traditional cyanoacrylate-containing compositionswhile curing through at least a photo-induced polymerization mechanism,thereby providing to the compositions (and cured reaction productsformed therefrom) the benefits and advantages of curing through such amechanism. More specifically, photocurable compositions according tothis invention cure rapidly, and in so doing minimize the opportunityfor undesirable blooming or crazing formation in the cured reactionproduct.

In another aspect of the present invention, there is provided a methodof polymerizing a photocurable composition by providing an amount of thecomposition to a desired surface and exposing the composition toradiation in an amount sufficient to effect cure thereof.

In yet another aspect of the present invention, there is provided thecured reaction product formed from a photocurable composition afterexposure thereof to a curingly effective amount of radiation.

The present invention will be more readily appreciated by those personsof skill in the art based on a reading of the detailed description ofthe invention which follows and the examples presented thereafter forillustrative purposes.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to photocurable compositions which include acyanoacrylate component or a cyanoacrylate-containing formulation, ametallocene component and a polymerizingly effective amount of aphotoinitiator.

The cyanoacrylate component or cyanoacrylate-containing formulationincludes cyanoacrylate monomers which may be chosen with a raft ofsubstituents, such as those represented by H₂C═C(CN)—COOR, where R isselected from C₁₋₅, alkyl, alkoxyalkyl, cycloalkyl, alkenyl, aralkyl,aryl, allyl and haloalkyl groups. Desirably, the cyanoacrylate monomeris selected from methyl cyanoacrylate, ethyl-2-cyanoacrylate, propylcyanoacrylates, butyl cyanoacrylates, octyl cyanoacrylates,allyl-2-cyanoacrylate, β-methoxyethyl-2-cyanoacrylate and combinationsthereof. A particularly desirable cyanoacrylate monomer for use hereinis ethyl-2-cyanoacrylate.

A variety of organometallic materials are also suitable for use herein.Those materials of particular interest herein may be represented bymetallocenes within structure I:

where

R₁ and R₂ may be the same or different and may occur at least once andup to as many as four times on each ring in the event of a five-memberedring and up to as many as five times on each ring in the event of asix-membered ring;

R₁ and R₂ may be selected from H; any straight- or branched-chain alkylconstituent having from 1 to about 8 carbon atoms, such as CH₃, CH₂CH₃,CH₂CH₂CH₃, CH(CH₃)₂, C(CH₃)₃ or the like; acetyl; vinyl; allyl;hydroxyl; carboxyl; —(CH₂)_(n)—OH, where n may be an integer in therange of 1 to about 8; —(CH₂)_(n)—COOR₃, where n may be an integer inthe range of 1 to about 8 and R₃ may be any straight- or branched-chainalkyl constituent having from 1 to about 8 carbon atoms; H; Li; Na; or—(CH₂)_(n′), where n′ may be an integer in the range of 2 to about 8;—(CH₂)_(n)—OR₄, wherein n may be an integer in the range of 1 to about 8and R₄ may be any straight- or branched-chain alkyl constituent havingfrom 1 to about 8 carbon atoms; or —(CH₂)_(n)—N′(CH₃)₃ X⁻, where n maybe an integer in the range of 1 to about 8 and X may be Cl⁻, Br⁻, I⁻,ClO₄ ⁻ or BF₄ ⁻;

Y₁ and Y₂ may not be present at all, but when at least one is presentthey may be the same or different and may be selected from H, Cl⁻, Br⁻,I⁻, cyano, methoxy, acetyl, hydroxy, nitro, trialkylamines,triaryamines, trialkylphospines, triphenylamine, tosyl and the like;

A and A′ may be the same or different and may be C or N;

m and m′ may be the same or different and may be 1 or 2; and

M_(e) is Fe, Ti, Ru, Co, Ni, Cr, Cu, Mn, Pd, Ag, Rh, Pt, Zr, Hf, Nb, V,Mo and the like.

Of course, depending on valence state, the element represented by M_(e)may have additional ligands—Y₁ and Y₂—associated therewith beyond thecarbocyclic ligands depicted above (such as where M_(e) is Ti and Y₁ andY₂ are Cl⁻).

Alternatively, metallocene structure I may be modified to includematerials such as:

where R₁, R₂, Y₁, Y₂, A, A′, m, m′ and M_(e) are as defined above. Aparticularly desirable example of such a material is where R₁ and R₂ areeach H; Y₁ and Y₂ are each Cl; A and A′ are each N; m and m′ are each 2and M_(e) is Ru.

Within metallocene structure I, well-suited metallocene materials may bechosen from within metallocene structure II:

where R₁, R₂ and M_(e) are as defined above.

Particularly well-suited metallocene materials from within structure Imay be chosen where R₁, R₂, Y₁, Y₂, m and m′ are as defined above, andM_(e) is chosen from Ti, Cr, Cu, Mn, Ag, Zr, Hf, Nb, V and Mo.

Desirably, the metallocene is selected from ferrocenes (i.e., whereM_(e) is Fe), such as ferrocene, vinyl ferrocenes, ferrocenederivatives, such as butyl ferrocenes or diarylphosphino metal-complexedferrocenes [e.g., 1,1-bis(diphenylphosphino) ferrocene-palladiumdichloride], titanocenes (i.e., where M_(e) is Ti), such asbis(η⁵-2,4-cyclopentadien-1-yl)-bis-[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium which is available commercially from Ciba-Geigy Corporation,Tarrytown, N.Y. under the tradename “IRGACURE” 784DC, and derivativesand combinations thereof. A particularly desirable metallocene isferrocene.

And bis-alkylmetallocenes, for instance, bis-alkylferrocenes (such asdiferrocenyl ethane, propanes, butanes and the like) are also desirablefor use herein, particularly since about half of the equivalent weightof the material (as compared to a non-bis-metallocene) may be employedto obtain the sought-after results, all else being unchanged. Of thesematerials, diferrocenyl ethane is particularly desirable.

Of course, other materials may be well-suited for use as the metallocenecomponent. For instance, M_(e)[CW₃—CO—CH═C(O⁻)—CW′₃]₂, where M_(e) is asdefined above, and W and W′ may be the same or different and may beselected from H, and halogens, such as F and Cl. Examples of suchmaterials include platinum (II) acetyl acetonate (“PtACAC”), cobalt (II)acetyl acetonate (“CoACAC”), nickel (II) acetyl acetonate (“NiACAC”) andcopper (II) acetyl acetonate (“CuACAC”). Combinations of those materialsmay also be employed.

A number of photoinitiators may be employed herein to provide thebenefits and advantages of the present invention to which reference ismade above. Photoinitiators enhance the rapidity of the curing processwhen the photocurable compositions as a whole are exposed toelectromagnetic radiation. Certain metallocenes, such as “IRGACURE”784DC, may serve a dual purpose as both metallocene and photoinitiator.

Examples of suitable photointiators for use herein include, but are notlimited to, photoinitiators available commercially from Ciba-GeigyCorp., Tarrytown, N.Y. under the “IRGACURE” and “DAROCUR” tradenames,specifically “IRGACURE” 184 (1-hydroxycyclohexyl phenyl ketone), 907(2-methyl-1-[4-(methylthio)phenyl]-2-morpholino propan-1-one), 369(2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone), 500(the combination of 1-hydroxy cyclohexyl phenyl ketone andbenzophenone), 651 (2,2-dimethoxy-2-phenyl acetophenone), 1700 (thecombination of bis(2,6-dimethoxybenzoyl-2,4,4-trimethyl pentyl)phosphineoxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one), and 819[bis(2,4,6-trimethyl benzoyl)phenyl phosphine oxide] and “DAROCUR” 1173(2-hydroxy-2-methyl-1-phenyl-1-propane) and 4265 (the combination of2,4,6-trimethylbenzoyldiphenyl-phosphine oxide and2-hydroxy-2-methyl-1-phenyl-propan-1-one); and the visible light [blue]photoinitiators, dl-camphorquinone and “IRGACURE” 784DC. Of course,combinations of these materials may also be employed herein.

Other photoinitiators useful herein include alkyl pyruvates, such asmethyl, ethyl, propyl, and butyl pyruvates, and aryl pyruvates, such asphenyl, benzyl, and appropriately substituted derivatives thereof.

Photoinitiators particularly well-suited for use herein includeultraviolet photoinitiators, such as 2,2-dimethoxy-2-phenyl acetophenone(e.g., “IRGACURE” 651), and 2-hydroxy-2-methyl-1-phenyl-1-propane (e.g.,“DAROCUR” 1173), bis(2,4,6-trimethyl benzoyl)phenyl phosphine oxide(e.g., “IRGACURE” 819), and the ultraviolet/visible photoinitiatorcombination of bis(2,6-dimethoxybenzoyl-2,4-,4-trimethylpentyl)phosphineoxide and 2-hydroxy-2-methyl-1-phenyl-propan-1-one (e.g., “IRGACURE”1700), as well as the visible photoinitiatorbis(η^(s)-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium(e.g., “IRGACURE” 784DC).

With respect to formulating photocurable compositions, generally thecomponents may be introduced to one another in any convenient order.Alternatively, it may be desirable to prepare a premix of themetallocene component and the photoinitiator component. In this way, aready made premix of those components may be added to the cyanoacrylatecomponent of the formulation to allow for a quick and easy one-partformulation of a photocurable composition prior to dispensing and curingthereof.

For packaging and dispensing purposes, it may be desirable forphotocurable compositions in accordance with the present invention to berelatively fluid and flowable. Variations in the viscosity thereof mayalso be desirable in certain applications and may be readily achievedthrough routine changes in formulation, the precise changes being leftto those persons of ordinary skill in the art.

For instance, ordinarily cyanoacrylate-containing compositions free froman added thickener or viscosity modifier are low viscosity formulations(such as in the range of 1 to 3 cps). While a composition with such a isviscosity (or one whose viscosity has been modified to be up to aboutfive times that viscosity) may be appropriate for a wicking applicationwhere a small gap exists between substrates to be bound (e.g., less thanabout 0.1 mils) and/or an application where enhanced cure speed isdesirable, such a viscosity may be too low for convenient use in certainindustrial applications. At least for this reason, the viscosity ofcyanoacrylate-containing compositions has at times been desirablymodified through, for instance, the addition of polymethylmethacrylatesand/or fumed silicas. See e.g., U.S. Pat. No. 4,533,422 (Litke) and Re.32,889 (Litke), the disclosures of each of which are hereby expresslyincorporated herein by reference.

A medium viscosity formulation (such as in the range of 100 to 300 cps)may be more appropriate in applications where greater control offlowability is desirable such as bonding together molded polymericparts. And a high viscosity formulation (such as in the range of 600 to1000 cps) may be more appropriate in applications involving poroussubstrates and/or substrates with larger gaps (such as greater thanabout 0.5 mils).

Of course, those of ordinary skill in the art should make appropriatedecisions regarding whether a viscosity modifier should be included inthe photocurable composition, and if so which one(s) and at what levelshould one be included to achieve the desired viscosity for the intendedapplications.

In addition, it may be desirable to toughen the cured photocurablecompositions of the present invention through the addition ofelastomeric rubbers such as is taught by and claimed in U.S. Pat. No.4,440,910 (O'Connor), the disclosure of which is hereby expresslyincorporated herein by reference. It may also be desirable to improvethe hot strength of the cured photocurable compositions by addition ofanhydrides, such as is taught by and claimed in U.S. Pat. No. 4,450,265(Harris) and the documents cited therein, the disclosures of each ofwhich are hereby expressly incorporated herein by reference.

Moreover, the compositions of the present invention may be rendered intoa thixotropic paste through addition of powdered organic fillers havinga particle size of about 2 to 200 microns as is taught by U.S. Pat. No.4,105,715 (Gleave) or thickened by a copolymer or terpolymer resin toimprove peel strength as is taught by U.S. Pat. No. 4,102,945 (Gleave),the disclosures of each of which are hereby incorporated herein byreference.

Further, the compositions of the present invention may be rendered moreresistant to thermal degradation at elevated temperature conditions bythe inclusion of certain sulfur-containing compounds, such assulfonates, sulfinates, sulfates and sulfites as set forth in U.S. Pat.No. 5,328,944 (Attarwala), the disclosure of which is hereby expresslyincorporated herein by reference. The inclusion of such compounds in thephotocurable compositions of the present invention renders thosecompositions well-suited for applications in which elevated temperatureconditions may be experienced, such as with potting compoundsparticularly where large cure through volume is present and non-tackysurfaces are desirably formed in less than about five seconds.

The sulfur-containing compounds effective for enhancing the thermalresistance of the cured cyanoacrylate polymer may be representedaccording to the formula:

where R¹ and R² are, respectively, monovalent and divalent hydrocarbongroups which may be optionally substituted with halogen, NO₂, oxo (═O),CN, alkoxy, hydroxy, acyloxy or SO₂ or interrupted by one or more etheroxygen atoms.

The sulfur-containing compounds are suitably employed at levels of about0.1-10% by weight of the inventive composition.

More specifically, the thermal resistance conferring compound used inthe inventive compositions, include by way of example, acyclic andcyclic sulfates, such as diphenyl sulfate, dibutyl sulfate; andcompounds, such as 1,3,2-dioxathiolene-4-ethyl-2,2-dioxide and thedi(cyclic sulfate) of 1,2,7,8-octane tetraol which have one or moregroups of the formula:

where R³ is independently H, alkyl or aryl; anhydrosulfites, such asα-hydroxyisobutynic acid anhydrosulfite; sulfoxides such asdibutylsulfoxide, di-α,α′-phenylethylsulfoxide andα-methylthioxo-butyrolactone; sulfites such as glycol sulfite, dimethylsulfite diethyl sulfite and o-phenylene sulfite; sulfonates, such asethyl methanesulfonate, ethyl trifluoromethane sulfonate, methylp-toluenesulfonate, n-butyl p-toluenesulfonate, benzylp-toluenesulfonate, α-methylbenzyl p-toluenesulfonate,α,α-dimethylbenzyl p-toluenesulfonate and the diethyl ester of acetonedisulfonic acid; and sulfinates such as methyl-p-toluenesulfonate.

These compounds are usefully employed at levels in the range of about0.1%-10% by weight of the inventive composition, preferably at least0.5% and more typically about 0.75%-5% by weight of the inventivecomposition.

The inclusion of such materials to a photocurable composition inaccordance with the present invention may provide a formulation havingparticular advantages for certain applications, and at least in the caseof viscosity modifiers should be appealing from a safety perspective asthe possibility is decreased of splashing or spilling the composition onexposed skin of the user or bystanders. In addition, since the parts tobe bonded with the inventive compositions are fixed by exposure to UVradiation, there is less of a chance for the assembler to touch orcontact an uncured fillet.

The relative amount of the various components of the photocurablecompositions according to this invention is a matter of choice left tothose persons of skill in the art, depending of course on the identityof the particular components chosen for a specific composition. As ageneral guide, however, it is desirable to include in the photocurablecompositions a metallocene, such as ferrocene, in an amount within therange of about 0.005% to about 4% or greater (desirably within the rangeof about 0.01% to about 1.5%) by weight of the total composition. It isalso desirable for the compositions to include a photoinitiator, such as“IRGACURE” 1700 or 819, or “DAROCUR” 1173, in an amount within the rangeof about 0.125% to about 10% by weight of the composition, with about 2%to about 4% or greater by weight of the total composition beingdesirable. The balance of the composition is composed predominantly of acyanoacrylate component, such as ethyl-2-cyanoacrylate. Of course, theamount of all the components together in the composition totals 100%.

A method of curing a photocurable composition in accordance with thisinvention is also provided herein, the steps of which include (a)providing onto a desired substrate an amount of a photocurablecomposition; and (b) subjecting the composition to radiation sufficientto effect cure thereof.

The amount of photocurable composition provided should be sufficient tocure and form an adequate bond to the substrate surfaces between whichit is applied. For instance, application of the photocurable compositionmay he achieved by dispensing the composition in drop-wise fashion, oras a liquid stream, brush-applied, dipping, and the like, to form a thinfilm. Application of the photocurable composition may depend on theflowability or viscosity of the composition. To that end, viscositymodifiers, as noted above, may be included in the composition.

In use, such compositions are desirably readily dispensed onto a portionof a desired surface of a substrate onto which is to be bonded a portionof another substrate. The photocurable composition may be applied tocertain portions of the substrate surface or over the entire surface ofthe substrate to be bonded, depending on the particular application.

The source of radiation emitting electromagnetic waves is selected fromultraviolet light, visible light, electron beam, x-rays, infraredradiation and combinations thereof. Desirably, ultraviolet light is theradiation of choice, with appropriate sources including “H”, “D”, “V”,“X”, “M” and “A” lamps, mercury arc lamps, and xenon arc lamps (such asthose commercially available from Loctite Corporation, Rocky Hill,Conn., Fusion UV Curing Systems, Buffalo Grove, Ill. or Spectroline,Westbury, N.Y.); microwave-generated ultraviolet radiation; solar powerand fluorescent light sources. Any of these electromagnetic radiationsources may use in conjunction therewith reflectors and/or filters, soas to focus the emitted radiation onto a specific portion of a substrateonto which has been dispensed a photocurable composition and/or within aparticular region of the electromagnetic spectrum. Similarly, theelectromagnetic radiation may be generated directly in a steady fashionor in an intermittent fashion so as to minimize the degree of heatbuild-up. Although the electromagnetic radiation employed to cure thephotocurable compositions into desired reaction products is oftenreferred to herein as being in the ultraviolet region, that is not tosay that other radiation within the electromagnetic spectrum may notalso be suitable. For instance, in certain situations, radiation in thevisible region of the electromagnetic spectrum may also beadvantageously employed, whether alone or in combination with, forinstance, radiation in the ultraviolet region. Of course, microwave andinfrared radiation may also be advantageously employed under appropriateconditions.

Higher or lower radiation intensities, greater or fewer exposuresthereto and length of exposure and/or greater or lesser distances of thesource of radiation to the composition may be required to completecuring, depending of course on the particular components of a chosencomposition.

More specifically with respect to radiation intensity, the chosen lampshould have a power rating of at least about 100 watts per inch (about40 watts per cm), with a power rating of at least about 300 watts perinch (about 120 watts per cm) being particularly desirable. Also, sincethe inclusion of a photoinitiator in the composition may shift thewavelength within the electromagnetic radiation spectrum at which cureoccurs, it may be desirable to use a source of electromagnetic radiationwhose variables (e.g., wavelength, distance, and the like) are readilyadjustable.

During the curing process, the composition will be exposed to a sourceof electromagnetic radiation that emits an amount of energy, measured inKJ/m², determined by parameters including: the size, type and geometryof the source; the duration of the exposure to electromagneticradiation; the intensity of the radiation (and that portion of radiationemitted within the region appropriate to effect curing); the absorbencyof electromagnetic radiation by any intervening materials, such assubstrates; and the distance the composition lies from the source ofradiation. Those persons of skill in the art should readily appreciatethat curing of the composition may be optimized by choosing appropriatevalues for these parameters in view of the particular components of thecomposition.

To effect cure, the source of electromagnetic radiation may remainstationary while the composition passes through its path. Alternatively,a substrate coated with the photocurable composition may remainstationary while the source of electromagnetic radiation passesthereover or therearound to complete the transformation from compositionto reaction product. Still alternatively, both may traverse one another,or for that matter remain stationary, provided that the photocurablecomposition is exposed to electromagnetic radiation sufficient to effectcure.

Commercially available curing systems, such as the “ZETA” 7200 or 7400ultraviolet curing chamber (Loctite Corporation, Rocky Hill, Conn.),Fusion UV Curing Systems F-300 B (Fusion UV Curing Systems, BuffaloGrove, Ill.), Hanovia UV Curing System (Hanovia Corp., Newark, N.J.),BlackLight Model B-100 (Spectroline, Westbury, N.Y.) and RC500 A PulsedUV Curing System (Xenon Corp., Woburn, Mass.), are well-suited for thepurposes described herein. Also, a Sunlighter UV chamber fitted with lowintensity mercury vapor lamps and a turntable may be employed herein.

The required amount of energy may be delivered by exposing thecomposition to a less powerful source of electromagnetic radiation for alonger period of time, through for example multiple passes, oralternatively, by exposing the composition to a more powerful source ofelectromagnetic radiation for a shorter period of time. In addition,each of those multiple passes may occur with a source at differentenergy intensities. In any event, those persons of skill in the artshould choose an appropriate source of electromagnetic radiationdepending on the particular composition, and position that source at asuitable distance therefrom which, together with the length of exposure,optimizes transformation. Also, it may be desirable to use a source ofelectromagnetic radiation that is delivered in an intermittent fashion,such as by pulsing or strobing, so as to ensure a thorough and completecure without causing excessive heat build-up.

In use, a photocurable composition in accordance with the presentinvention may be dispensed, such as in the form of a thin film ordroplet, onto a desired substrate. Substrates onto which thephotocurable composition of the present invention may be applied may bechosen from a vast selection of different materials; basically, anymaterial with which cyanoacrylates may be used is suitable as well foruse herein. See supra.

Desirable choices among such materials include acrylics, epoxies,polyolefins, polycarbonates, polysulfones (e.g., polyether sulfone),polyvinyl acetates, polyamides, polyetherimides, polyimides andderivatives and co-polymers thereof with which may be blended orcompounded traditional additives for aiding processibility or modifyingthe physical properties and characteristics of the material to be usedas a substrate. Examples of co-polymers which may be employed assubstrates include acrylonitrile-butadiene-styrene,styrene-acrylonitrile cellulose, aromatic copolyesters based onterephthallic acid, p,p-dihydroxybiphenyl and p-hydroxy benzoic acid,polyalkylene (such as polybutylene or polyethylene)terephthalate,polymethyl pentene, polyphenylene oxide or sulfide, polystyrene,polyurethane, polyvinylchloride, and the like. Particularly, desirableco-polymers include those which are capable of transmitting UV and/orvisible radiation. Of course, other materials may also be employed assubstrates, such as metals, like stainless steel.

The composition-coated substrate may be positioned within anelectromagnetic radiation curing apparatus, such as the “ZETA” 7200ultraviolet curing chamber, equipped with an appropriate source ofelectromagnetic radiation, such as ultraviolet radiation, at anappropriate distance therefrom, such as within the range of about 1 to 2inches (2.54 to 5.08 cm), with about 3 inches (7.62 cm) being desirable.As noted above, the composition-coated substrate may remain in positionor may be passed thereunder at an appropriate rate, such as within therange of about 1 to about 60 seconds per foot, with about 5 seconds perfoot being desirable. Such passage may occur one or more times, or asneeded to effect cure of the composition on the substrate. The length ofexposure may be in the range of a few seconds or less (for one timeexposure) to tens of seconds or longer (for either a one time exposureor a multiple pass exposure) if desired, depending on the depth of thecomposition to be cured and of course on the components of thecomposition themselves.

A reaction product is also of course provided by the teaching of thisinvention. The reaction product is formed from photocurable compositionsafter exposure thereof to electromagnetic radiation sufficient to effectcure of the composition. The reaction product is formed rapidly, andordinarily and desirably without observed formation of blooming orcrazing, see infra.

The reaction product of the photocurable composition may be prepared bydispensing in low viscosity or liquid form a photocurable composition inaccordance with the present invention onto a substrate and mating thatsubstrate with a second substrate to form an assembly. Thereafter,exposure to electromagnetic radiation on at least one substrate of theassembly for an appropriate period of time should transform thephotocurable composition into an adhesive reaction product.

It is also within the scope of the present invention for reactionproducts to be prepared from a photocurable composition separately fromthe device, and thereafter positioned on a substrate surface with whichit is to be used. In this manner, such reaction products may desirablybe fabricated, for instance, into a film or tape, such as an adhesivefilm or a coating film, which when applied to a chosen substrate willbond thereto. Many known film manufacturing processes may be employed tomanufacture into films photocurable compositions in accordance with thepresent invention, including calendaring, casting, rolling, dispensing,coating, extrusion and thermoforming. For a non-exhaustive descriptionof such processes, see Modern Plastics Encyclopedia 1988, 203-300,McGraw-Hill Inc., New York (1988). With respect to dispensing orcoating, conventional techniques, such as curtain coating, spraycoating, dip coating, spin coating, roller coating, brush coating ortransfer coating, may be used.

A film of the photocurable composition may be prepared by extrusion orcalendaring, where cure occurs by exposure to electromagnetic radiationprior to, contemporaneously with, or, if the composition is sufficientlyviscous, after passing through the extruder or calendar. Thereafter, thefilm may be placed between the desired substrates, and construction ofthe device may be completed.

The viscosity of the photocurable composition may be controlled ormodified to optimize its dispensability by, in addition to inclusion ofan appropriate material to alter the viscosity thereof as noted above,adjusting the temperature of (1) the composition itself, or (2) thesubstrates on which the composition may be placed to assemble thedevice. For example, the temperature of the composition or thesubstrate(s) or combinations thereof may be decreased to increase theviscosity of the composition. In this way, the uniformity on thesubstrate of the dispensed photocurable composition may be enhancedusing lamination techniques, centrifuge techniques, pressure appliedfrom the atmosphere (such as with vacuum bagging), pressure applied froma weighted object, rollers and the like.

The substrates onto which the photocurable compositions of the presentinvention are intended to be dispensed may be constructed from thelitany of materials recited supra, which may be substantially inflexibleas well as flexible. The type of substrate chosen with respect toflexibility will of course depend on the application for which it is tobe used. More specifically, the substrates may be constructed fromsubstantially inflexible materials, such as glass, laminated glass,tempered glass, optical plastics, such as polycarbonates, acrylics andpolystyrenes, and other alternatives as noted supra; and flexiblematerials, such as “MYLAR” film or polyolefin, such as polyethylene orpolypropylene, tubing.

The choice of substrate material may influence the choice of processingtechnique used to prepare the photocurable composition into the curedreaction product or the type of device assembled. For example, whenassembling a device from at least one flexible substrate, a compositionmay be advantageously applied to an end portion of the flexiblesubstrate and allowed to wick along that end portion through a portionof another substrate, which is dimensioned to receive that end portionof the flexible substrate. A particular example of such an applicationis polyolefin tubing intended for medical application, one end portionof which is dimensioned for receiving by an acrylic luer housing.

In addition, roll-to-roll systems may be employed where flexiblesubstrates are released from rolls (that are aligned and rotate indirections opposite to one another), and brought toward one another in aspaced-apart relationship. In this way, the photocurable composition maybe dispensed or injected onto one of the flexible substrates at a pointwhere the two flexible substrates are released from their respectiverolls and brought toward one another, while being contemporaneouslyexposed to electromagnetic radiation for a time sufficient to cure thecomposition into an adhesive reaction product.

The dispensing of the composition may be effected through an injectionnozzle positioned over one of the rolls of flexible substrate. Bypassing in the path of the nozzle as a continuously moving ribbon, aflexible substrate may be contacted with the composition in anappropriate amount and positioned on the flexible substrate.

Since the photocurable compositions of the present invention cure toform reaction products through, as their description connotes, aphoto-initiated mechanism, the composition and the surface of thesubstrate on which the composition is placed should be exposed to thesource of electromagnetic radiation. The choice of substrate may affectthe rate and degree at which cure occurs of the photocurablecompositions of the present invention. For instance, it is desirable forthe substrates to be bonded together to be substantially free ofelectromagnetic radiation-absorbing capabilities. That is, the greaterdegree of electromagnetic radiation transmitting capability thesubstrate possesses, the greater the rate and degree of cure of thecomposition, all else being equal of course.

Blooming or crazing may be observed when compositions cure into reactionproducts and the cure itself is incomplete. That is, blooming refers tothe evaporation of cyanoacrylate monomer (due to its relatively highvapor pressure) from uncured fillets, the result of which is formationof a precipitate on surfaces adjacent to the bond line which are alsoobserved as a white haze. Crazing refers to the formation of stresscracks on certain synthetic materials, such as polycarbonates, acrylicsand polysulfones, due in this instance to the presence thereon ofcyanoacrylate monomer.

The result of incomplete curing may be observed with respect to adhesiveuses of the photocurable composition as adhesive or cohesive failure ofthe cured composition when applied to or between substrates. Suchobservations may be minimized or even eliminated by usingelectromagnetic radiation transmitting (as contrasted to absorbing)substrates and placing the source of electromagnetic radiation at astrategic location so as to improve the degree of electromagneticradiation to which the composition on the substrate is exposed.Similarly, additional sources of electromagnetic radiation, or as statedabove reflectors which redirect onto desired portions of the substratestray or errant electromagnetic radiation, may be employed to furtherenhance cure.

Accordingly, the compositions of this invention provide a number ofbenefits and advantages. These include: a built-in secondary cure system(i.e., photo-initiation in addition to the ordinary cyanoacrylateanionic initiation), which is particularly attractive in thoseapplications where certain of the substrates which may be used in theassembly do not allow the transmission of light, rendering another typeof adhesive (such as a dual cure acrylic adhesive) less desirablebecause a secondary heating step would then be required; elimination ofa substrate primer step, which obviates the use of often flammablematerials and invites automated processes; and improves the cure thoughgap.

In view of the above description of the present invention, it is evidentthat a wide range of practical opportunities is provided by the teachingherein. Certain of those practical opportunities are exemplified below,as are many of the advantages and benefits of the present invention.However, the invention as so exemplified is for illustrative purposesonly and is not to be construed in any way as limiting the broad aspectsof the teaching herein provided.

EXAMPLES Example 1

A photocurable composition in accordance with the present invention wasprepared from about 95.9 grams of ethyl-2-cyanoacrylate, about 0.1 gramsof ferrocene and about 4 grams of “DAROCUR” 1173 as a photoinitiator.Typically, commercially available cyanoacrylate-containing compositions(such as “PRISM” Adhesive 4061, commercially available from LoctiteCorporation, Rocky Hill, Conn.) are stabilized against premature anionicpolymerization by the addition of an acidic material, such as borontrifluoride or methane sulfonic acid. In this example, therefore, theethyl cyanoacrylate contained about 20 ppm of boron trifluoride as anacid anionic stabilizer. Of course, greater or lesser amounts of borontriflouride or other acidic anionic stabilizers may be added for suchpurpose.

In one instance, the three components were added directly to apolyethylene vessel and mixed for a period of time of about thirtyminutes at room temperature. In another instance, the cyanoacrylate wasadded to the polyethylene vessel, and thereafter a premix of theferrocene in the “DAROCUR” photoinitiator was added to the cyanoacrylatealready in the vessel. Mixing in this latter instance was also allowedto continue for a period of time of about thirty minutes at roomtemperature.

Once the photocurable composition was prepared, a drop or bead (about0.2 grams) thereof was dispensed using a polyethylene pipet onto anultraviolet transmitting acrylic substrate (whose dimensions were about1×1×0.25 inches, such as those available commercially from IndustrialSafety Co.). More specifically, the composition was applied to one endportion of a substrate and thereafter a second substrate (each of whichbeing constructed from the same material and having the same dimensions)was placed in a laterally displaced, offset position with respectthereto so as to cover that portion of the first substrate onto whichthe composition was placed. This application was performed intriplicate.

The two substrates were then clamped together using a small alligatorclamp to form a test piece assembly, and thereafter introduced into a“ZETA” 7200 ultraviolet curing chamber, equipped with a five inch mediumpressure mercury arc lamp (emitting light of a wavelength of about 300to 365 nm). The clamped assembly was placed in the chamber under thelamp at a distance of about 2 to 3 inches, and exposed to theultraviolet light emitted by the lamp for a period of time of from aboutfive to about fifteen seconds as reflected below in Table 1.

After the indicated exposure time, the once-liquid composition wasobserved to have cured into a solid reaction product. The thickness ofthe cured material, or the bond line, was measured and determined to beabout 1-3 mils. The data presented below in Table 1 reflects valuesobtained after a period of time of about 24 hours at ambient temperatureconditions prior to testing.

Shear strength tests in accordance with the protocol set forth in ASTMD-1002 were performed on the cured test piece using an Instron Universaltester (Model 4206, Instron, Canton, Mass.). The Instron tester was usedto measure the force required to separate those test pieces from oneanother. Instron measurements, commonly in the range of about 2500 toabout 5000 psi, were obtained. The force measured translates into thebond strength of the cured reaction product, expressed in terms ofpounds per square inch (“psi”).

The limiting feature of the cured composition of the present inventionappears to be the strength of the substrate on which it is applied andcured. The average measurements from the three test piece assemblyspecimens are presented below in Table 1.

The data presented for Sample Nos. 1-3 in Table 1 reflect compositionswhich were subjected to varying initial exposures to electromagneticradiation and the shear strengths demonstrated by the reaction productas a result after a period of time of about 24 hours prior to Instrontesting. A second photocurable composition in accordance with thepresent invention was prepared in the same manner with about 2 grams of“IRGACURE” 651 as a replacement for the “DAROCUR” photoinitiator, withthe balance of the composition coming from additional “PRISM” Adhesive.Sample Nos. 4-6 in Table 1 reflect this second composition which weresubjected to the indicated varying initial exposures to electromagneticradiation.

TABLE 1 Sample Radiation Exposure Shear Strength No. (secs) (after 24hrs, psi) 1  5 4057 2 10 3835 3 15 4846 4  5 4984 5 10 4293 6 15 3062

Tables 2a and 2b below are to be construed together and set forthseveral other photocurable composition formulations in accordance withthe present invention prepared from “PRISM” Adhesive 4061 cyanoacrylateand 0.1% by weight ferrocene with the listed photoinitiators and amountsthereof, the cure process employed and certain properties andcharacteristics of the reaction products formed therefrom. Each of theseformulations (i.e., Sample Nos. 7-10) was allowed to cure completely fora period of time of about 24 hours after initial exposure to ultravioletlight. The shear strength of the reaction products formed from thosecured formulation is represented in Table 2b.

TABLE 2a Sample Photoinitiator Rad. Cure Rad. Exp. No. Type Amt Type(secs) 7 “DAROCUR” 1173 4% UV 10 8 “IRGACURE” 651 2% UV  5 9 “IRGACURE”1700 2% UV/VIS  2 10  “PRISM” Adh. 4061 — — — (control)

TABLE 2b Shear strength (psi) after 1-3 min after 24 hours SampleSubstrate Type. Substrate Type No. UV trans UV abs UV trans UV abs 73152  926  3591 2800 8 3352 1208  3021 3000 9 3292 2672 3,292 3198 10  42  147  1724 2624

In Table 2b, the shear strength was measured after exposure toelectromagnetic radiation after a period of time of about 1 to about 3minutes had elapsed and then again after a period of time of about 24hours at ambient temperature conditions. Plainly, the shear strengthmeasurements from the test piece assemblies constructed with thecomposition containing the “IRGACURE” 1700 photoinitiator (Sample No. 9)demonstrated a relatively small difference between test piece assembliesconstructed from UV transmitting and UV absorbing substrates. And theshear strength measurements from test piece assemblies constructed withthe UV absorbing substrates and the composition containing the“IRGACURE” 1700 photoinitiator was superior to that measured from thecompositions containing either of the other twophotoinitiators—“DAROCUR” 1173 (Sample No. 7) or “IRGACURE” 651 (SampleNo. 8)—after the 1-3 minute time period indicated above. However, aftera cure of about 24 hours, the measurements from each of the test pieceassemblies constructed from UV transmitting or UV absorbing substratesand from each of the above-listed photoinitiators were all substantiallywithin the same range, which was well above that of the control—“PRISM”Adhesive 4061 (Sample No. 10).

Example 2

In this example, a photoinitiator was used in the formulation which iscapable of initiating polymerization irrespective of whether thesubstrate used is constructed from a UV transmitting material or a UVabsorbing material. That is, the photoinitiator may be initiated byradiation in the visible region of the electromagnetic spectrum.

More specifically, three formulations were prepared from “PRISM”Adhesive 4061 together with about 0.1% by weight of ferrocene and about0.5% by weight to about 2% by weight of “IRGACURE” 1700 as aphotoinitiator. The amount of “PRISM” Adhesive 4061 (containingethyl-2-cyanoacrylate) chosen is within the range of about 97.9% byweight to about 99.4% by weight of the composition. A fourth formulationconsisted only of the “PRISM” Adhesive 4061 and was used as a control.

The formulations were prepared and applied to “s/p” micro slides(commercially available from Baxter Corporation, Deerfield, Ill.), whichwere then positioned in the “ZETA” 7200 UV curing chamber. Theformulations were each observed to cure on the glass slides in a timeperiod of about 2 to 3 seconds.

The formulations were then applied to acrylic substrates, both of the UVabsorbing and the UV transmitting type. The formulations were applied totwo sets of test piece specimens in triplicate of both UV absorbingacrylic substrates and UV transmitting acrylic substrates, which weremated to form test piece assemblies. The so-formed assemblies were thenpositioned in the UV curing chamber and exposed to UV radiation for thefollowing time periods: about 1, 2 and 5 seconds. Thereafter, the testpiece assemblies were maintained at ambient temperature conditions for aperiod of time of about 1 to 3 minutes and shear strength measurementsof each test piece assembly were determined using the Instron Universaltester, as described in Example 1, supra. The second set of triplicatespecimens was allowed to cure further at ambient temperature conditionsfor a period of time of about 24 hours. Failure in these specimens mayoccur due either to substrate failure (e.g., substrate fracture),cohesive failure (e.g., where a portion of the photocurable compositionseparates due to the applied force on surfaces of both substrates) oradhesive failure (e.g., where the composition separates due to theapplied force on a surface of one substrate).

The first formulation contained about 2% by weight of “IRGACURE” 1700,and the UV transmitting test piece which was exposed to UV radiation for1 second demonstrated a shear strength of about 2552 psi with adhesiveand cohesive failure; the corresponding UV absorbing test piece assemblydemonstrated a shear strength of about 864 psi with cohesive failure.The UV transmitting test piece which was exposed to UV radiation for 2seconds demonstrated a shear strength of about 3292 psi with adhesiveand substrate failure; the corresponding UV absorbing test piecedemonstrated a shear strength of about 2672 psi with adhesive andsubstrate failure. The UV transmitting test piece which was exposed toUV radiation for 5 seconds demonstrated a shear strength of about 2910psi with adhesive failure; the corresponding UV absorbing test piecedemonstrated a shear strength of about 1698 psi with adhesive andsubstrate failure.

The UV transmitting test piece which was exposed to UV radiation for 1second and thereafter allowed to cure further for 24 hours demonstrateda shear strength of about 2572 psi with adhesive failure; thecorresponding UV absorbing test piece assembly demonstrated a shearstrength of about 2466 psi with adhesive failure. The UV transmittingtest piece which was exposed to UV radiation for 2 seconds andthereafter allowed to cure further for 24 hours was observed to notchange with respect to shear strength; the corresponding UV absorbingtest piece demonstrated a shear strength of about 3198 psi withsubstrate failure. The UV transmitting test piece which was exposed toUV radiation for 5 seconds and thereafter allowed to cure further for 24hours demonstrated a shear strength of about 3812 psi with substratefailure; the corresponding UV absorbing test piece demonstrated a shearstrength of about 3502 psi with substrate failure.

The second formulation contained about 1% by weight of “IRGACURE” 1700,and the UV transmitting test piece which was exposed to UV radiation for1 second demonstrated a shear strength of about 1272 psi with adhesivefailure; the corresponding UV absorbing test piece assembly demonstrateda shear strength of about 430 psi with cohesive failure. The UVtransmitting test piece which was exposed to UV radiation 2 secondsdemonstrated a shear strength of about 2808 psi with adhesive andcohesive failure; the corresponding UV absorbing test piece demonstrateda shear strength of about 2334 psi with adhesive and substrate failure.The UV transmitting test piece which was exposed to UV radiation for 5seconds demonstrated a shear strength of about 2208 psi with adhesivefailure; the corresponding UV absorbing test piece demonstrated a shearstrength of about 1832 psi with adhesive and cohesive failure.

The UV transmitting test piece which was exposed to UV radiation for 1second and thereafter allowed to further cure for 24 hours demonstrateda shear strength of about 2828 psi with adhesive and substrate failure;the corresponding UV absorbing test piece assembly demonstrated a shearstrength of about 1742 psi with cohesive failure. The UV transmittingtest piece which was exposed to UV radiation 2 seconds and thereafterallowed to cure further for 24 hours demonstrated a shear strength ofabout 2808 psi with adhesive and cohesive failure; the corresponding UVabsorbing test piece demonstrated a shear strength of about 2538 psiwith adhesive and substrate failure. The UV transmitting test piecewhich was exposed to UV radiation for 5 seconds and thereafter allowedto cure further for 24 hours demonstrated a shear strength of about 2004psi with cohesive failure; the corresponding UV absorbing test piecedemonstrated a shear strength of about 3524 psi with substrate failure.

The third formulation contained about 0.5% by weight of “IRGACURE” 1700,and the UV transmitting test piece which was exposed to UV radiation for1 second demonstrated a shear strength of about 1776 psi with adhesivefailure; the corresponding UV absorbing test piece assembly was notobserved to cure. The UV transmitting test piece which was exposed for 2seconds demonstrated a shear strength of about 1830 psi with cohesivefailure; the corresponding UV absorbing test piece demonstrated a shearstrength of about 654 psi also with cohesive failure. The UV,transmitting test piece which was exposed to UV radiation for 5 secondsdemonstrated a shear strength of about 2064 psi with adhesive andcohesive failure; the corresponding UV absorbing test piece demonstrateda shear strength of about 1904 psi with adhesive and cohesive failure.

The UV transmitting test piece which was exposed to UV radiation for 1second and thereafter allowed to cure further for 24 hours demonstrateda shear strength of about 3124 psi with adhesive and substrate failure;the corresponding UV absorbing test piece assembly was again observednot to cure. The UV transmitting test piece which was exposed for 2seconds and allowed to cure further for 24 hours demonstrated a shearstrength of about 1830 psi with cohesive failure; the corresponding UVabsorbing test piece demonstrated a shear strength of about 2820 psiwith adhesive and substrate failure. The UV transmitting test piecewhich was exposed to UV radiation for 5 seconds and thereafter allowedto cure further for 24 hours demonstrated a shear strength of about 2190psi with adhesive and cohesive failure; the corresponding UV absorbingtest piece demonstrated a shear strength of about 3128 psi withsubstrate failure.

As a control composition, “PRISM” Adhesive 4061 cyanoacrylate adhesivewas also applied to both UV transmitting and UV absorbing test pieces.Exposure of both UV transmitting and UV absorbing test pieces to UVradiation for 5 seconds resulted in shear strength measurements of about13 psi and 14 psi, respectively. Values of this order of magnitudeeffectively mean that the composition did not cure. After a period ofabout 24 hours at ambient temperature conditions, the UV transmittingtest piece assembly demonstrated a shear strength of about 1724 psi andthe UV absorbing test piece assembly demonstrated a shear strength ofabout 2624 psi.

Example 3

In this example, additional compositions in accordance with the presentinvention were prepared and evaluated for their speed of cure,stability, and bond strength.

Table 3 below shows the components of these compositions.

TABLE 3 Sample Amounts No. Components (wt %) 11 Ethyl-2-cyanoacrylate99.495 Ferrocene 0.005 “IRGACURE” 819 0.5 12 Ethyl-2-cyanoacrylate 98.99Cp₂HfCl₂ 0.0114 “IRGACURE” 1700 1 13 Ethyl-2-cyanoacrylate 99.48Py₂RuCl₂ 0.0228 “IRGACURE” 1700 0.5 14 Ethyl-2-cyanoacrylate 98.99Diferrocenyl ethane 0.0108 “IRGACURE” 1700 1 15 Ethyl-2-cyanoacrylate98.98 Cp₂MoCl₂ 0.0166 “IRGACURE” 1700 1 16 Ethyl-2-cyanoacrylate 98.98Cp₂TiCl₂ 0.016 “IRGACURE” 1700 17 Ethyl-2-cyanoacrylate 98.97 Cp₂ZrCl₂0.0288 “IRGACURE” 1700 1 18 Ethyl-2-cyanoacrylate 99.48 PtACAC 0.02“IRGACURE” 1700 0.5 19 Ethyl-2-cyanoacrylate 98.99 Ferrocene 0.01 Methylpyruvate 1

In Table 3, Cp₂ represents dicyclopentadienyl and Py₂ representsbis(2-pyridyl). In addition, to the ethyl-2-cyanoacrylate has been addedabout 50 ppm of BF₃ and about 1000 ppm of hydroquinone to minimizepremature anionic polymerization and free-radical formation,respectively.

Sample Nos. 11-19 were prepared along the lines of the samples describedin Example 1, supra.

Once prepared, about 10 mg of each sample was placed in an aluminum panand exposed to UV radiation emitted by a medium pressure mercury lamp(10 mW/cm² intensity at a 365 nm wavelength). The exposure occurred fora period of time of about 10 minutes under isothermal conditions at atemperature of about 30° C.

The data shown below in Table 4 provides information on Sample Nos.11-19 regarding their ability to cure when exposed to electromagneticradiation. The response for these samples was determined with a DuPont930 Differential Photo Calorimeter (“DPC”) to which was attached anOriel 68805 universal power supply.

The induction time and peak max time is the time of UV exposure requiredto induce a photo-curing reaction and to reach a reaction maximum,respectively. These data are measured by onset and peak time of thereaction enthalphy (or exothermic photo-curing reaction). Higherenthalphy indicates the sample has a greater reactivity. Of course, afaster curing sample will have a shorter induction time, a peak max timeand a higher enthalphy. For example, Sample 11 required 1.1 seconds ofsuch UV exposure to induce UV curing, 4 seconds to reach a UV curingreaction maximum and generated 164 J/G of exotheric heat.

TABLE 4 Induction Peak Sample Time Max Enthalpy No. (secs) (secs) (J/G)11 1.1 4 164 12 14.5 629 406 13 6.1 11.2 278 14 1.7 4.8 204 15 4.3 8.2277 16 16.6 531 224 17 18.6 221 309 18 12.2 88 419 19 24 172 355

As a control, ethyl-2-cyanoacrylate was exposed to UV radiation underthe same conditions as the other samples, and no polymerization reactionwas observed to occur.

Example 4

In this example, one-part compositions according to the presentinvention were prepared with a variety of viscosities andphotoinitiators for comparative purposes.

Table 5 below shows the components of these compositions.

TABLE 5 Sample Amounts No. Components (wt %) 20 Ethyl-2-cyanoacrylate88.995 Ferrocene 0.005 PMMA 10.5 “IRGACURE” 1700 0.5 21Ethyl-2-cyanoacrylate 92.495 Ferrocene 0.005 PMMA 7 “IRGACURE” 1700 0.522 Ethyl-2-cyanoacrylate 92.495 Ferrocene 0.005 PMMA 7 “IRGACURE” 8190.5 23 Ethyl-2-cyanoacrylate 98.995 Ferrocene 0.005 “DAROCUR” 1173 1 24Ethyl-2-cyanoacrylate 99.495 Ferrocene 0.005 “IRGACURE” 1700 0.5

In Table 5, PMMA represent poly(methyl methacrylate).

Sample Nos. 20-24 were also prepared along the lines of the samplesdescribed in Example 1, supra.

Once prepared, about 10 mg of each sample was placed in an aluminum panand exposed to UV radiation emitted by a medium pressure mercury lamp(10 mw/cm² intensity at a 365 nm wavelength). The exposure occurred fora period of time of about 10 minutes under isothermal conditions at atemperature of about 30° C.

The data shown below in Table 6 provides information on Sample Nos.20-24 regarding their ability to cure when exposed to electromagneticradiation. The response for these samples was again determined with theDuPont 930 DPC.

As a control, a PMMA-thickened ethyl-2-cyanoacrylate was exposed to UVradiation under the same conditions as the other samples, and nopolymerization reaction was observed to occur.

TABLE 6 Induction Peak Sample Time Max Enthalpy No. (secs) (secs) (J/G)20 1.9 4.6 252 21 17 5 208 22 1.1 4 203 23 5 17 282 24 1.3 4.2 194

The bond strength for the cured reaction product of each sample is setforth in Table 7 below.

TABLE 7 Block Sheer Strength Sample @ 2 mins @ 24 hrs No. RT Cure RTCure 20 1407 1637 21 1416 1951 22 1851 1815 23 — — 24 — —

Example 5

The photocurable compositions of the present invention may be used infar flung manufacturing opportunities.

For instance, a variety of equipment for the medical industry may bemanufactured using the inventive compositions, including, but notlimited to, needles, tubesets, makes and catheters.

With respect to needles, syringes, lancets, hypodermics, injectors,bodily fluid (such as blood or urine) collector sets, cannula/hubassemblies and cannula/tube assemblies, such as those to be used inconnection with dialysis processes are but a few examples of needles forthe medical industry which may be manufactured with the composition ofthis invention.

Generally, in the manufacture of needles for which a cannula is insertedinto a cavity within a hub and is to be affixed therein, dispensing apre-determined amount of the inventive compositions and subjecting theassembly to UV radiation allows a quick fixation which will cure throughthe shadow area by the ordinary cyanoacrylate anionic cure mechanism toa full-strength bond within 24 hours.

Moreover, with respect to those needle assemblies which aim at beingtamper proof and which provide a cap, the inventive composition may beplaced at the juncture between the cap and the collar in which may beplaced a hub.

In addition, with respect to tubesets, intravenous sets, fluid deliveryand withdrawl sets (such as drug delivery and blood withdrawal sets) andsuction tubes are but a few examples of tubesets for the medicalindustry which may be manufactured with the composition of thisinvention.

In such instances, tubesets and connectors may be assembled with theinventive compositions by inserting one end of the tubing into theappropriate housing of a connector.

Avoiding the use of a primer composition is particularly attractivesince solvents used in conventional primer compositions may cause thereaction product formed from conventional reactive adhesive compositionsto be brittle and more susceptible to stress cracking. In contrast, thephotocurable feature of the compositions of this invention allow theparts to become fixtured quickly, thereby permitting the conventionalanionic-initiated cyanoacrylate cure mechanism to occur without fear ofcompromising the integrity of the bond formed.

Also, with respect to masks, anesthesia, face and surgical masks are buta few examples of equipment worn by providers of medical services, whichmay be manufactured with the composition of this invention.

And, with respect to catheters, angioplast and balloon-type cathetersare but a few examples of types of catheters, which may be manufacturedwith the compositions of this invention.

Of course, other applications for the compositions of the presentinvention exist beyond those specifically exemplified above and arecontemplated within the scope thereof, including, but not limited to,silk screening or disc drive applications; holographic applicationswhere a phase hologram is prepared for optical information storage;magnetic sensor applications for door/window alarms where the magnet isbonded to the sensor housing using the inventive compositions so thatthe dead space within the housing is filled; attaching gauge needles tosupport posts (e.g., in automotive applications); bonding togethercardboard holding cartridges for batteries; loud speaker assembly [seee.g., in the context of Loctite “PRISM” Adhesive 4204, “Beyond a SimpleBond—Benefits of Adhesives Extend to Product and Process”, Design News(Jan. 20, 1997)] for which the inventive compositions may be used in atleast five aspects of the assembly—attaching the spider (which alignsthe voice coil to the magnet) to the frame, attaching the surround(which is connected to the case) to the frame, tacking the lead wires,attaching the dust cap to the cone, and attaching the voice coil to thespider and the cone; lens bonding applications; applications whereblooming and crazing would be aesthetically unacceptable from acommercial perspective, such as in jewelry fabrication and repairapplications where use of a thick fillet of cured material (such as areaction product of the inventive compositions) would be desirable forstructural mounting; electronic potting applications; and otherapplications where it would be desirable to obviate the need for the useof a primer material (which may be costly, contain an ozone-depletingmaterial and/or may complicate the assembly process), for instance, thefastening of electronic wire tacking, and the like.

Also, electronic applications where outgassing is a conventionalrecurring problem may employ the photocurable compositions of thisinvention to decrease the heating time required to obtain a fully-curedreaction product of the composition, thereby decreasing outgassing whichmay occur.

While the present invention has been exemplified as shown above, it isclear that variations are also intended to be within the spirit andscope of the present invention and may be practiced in accordanceherewith, with only routine, rather than undue, experimentation. Anyvariations and equivalents should provide suitable, if not comparableresults, when viewed in connection with the results obtained from theabove examples. Accordingly, such variations and equivalents are alsointended to be encompassed by claims which follow.

What is claimed is:
 1. A composition comprising: (a) a 2-cyanoacrylatemonomer of the formula H₂C═C(CN)—COOR, wherein R is selected from thegroup consisting of C₁₋₁₅ alkyl, alkoxyalkyl, cycloalkyl, alkenyl,aralkyl, aryl, allyl and haloalkyl groups, (b) a metallocene component,(c) a polymerisingly effective amount of a photoinitiator componentother than the metallocene component to render the composition capableof photocuring in air upon exposure to at least one type ofelectromagnetic radiation selected from the group consisting ofultraviolet light, visible light, electron beam, x-ray and infraredradiation, (d) one or more sulfur-containing compounds selected from thegroup consisting of sulfonates, sulfinates, sulfates, and sulfites, and(e) polymethyl methacrylate.
 2. The composition according to claim 1,wherein the 2-cyanoacrylate monomer is selected from the groupconsisting of methyl cyanoacrylate, ethyl-2-cyanoacrylate, propylcyanoacrylates, butyl cyanoacrylates, octyl cyanoacrylates,allyl-2-cyanoacrylate, β-methoxyethyl-2-cyanoacrylate and combinationsthereof.
 3. The composition according to claim 1, wherein the2-cyanoacrylate monomer is ethyl-2-cyanoacrylate.
 4. The compositionaccording to claim 1, wherein the metallocene component includesmaterials within the following structure:

wherein R₁ and R₂ occur at least once on each ring, are the same ordifferent and are selected from the group consisting of H; any straight-or branched-chain alkyl constituent having from 1 to about 8 carbonatoms; acetyl; vinyl; allyl; hydroxyl; carboxyl; —(CH₂)_(n)—OH, whereinn is an integer in the range of 1 to about 8; —(CH₂)_(n)—COOR₃, whereinn is an integer in the range of 1 to about 8 and R₃ is a member selectedfrom the group consisting of H; any straight- or branched-chain alkylconstituent having from 1 to about 8 carbon atoms; —(CH₂)_(n′), whereinn′ is an integer in the range of 2 to about 8; and —(CH₂)_(n)—OR₄,wherein n is an integer in the range of 1 to about 8 and R₄ is anystraight- or branched-chain alkyl constituent having from 1 to about 8carbon atoms; Y₁ and Y₂ are optional and when present at least once arethe same or different and are selected from the group consisting of H,Cl, Br, I, cyano, methoxy, acetyl, hydroxy, nitro, trialkylamines,triaryamines, trialkylphospines, triphenylamine, and tosyl; A and A′ arethe same or different and are C or N; m and m′ are the same or differentand are 1 or 2; and M_(e) is a member selected from the group consistingof Fe, Ti, Ru, Co, Ni, Cr, Cu, Mn, Pd, Ag, Rh, Pt, Zr, Hf, Nb, V and Mo.5. The composition according to claim 1, wherein the metallocenecomponent includes materials within the following structure:

wherein R₁ and R₂ are the same or different, and each is a memberselected from the group consisting of H; any straight- or branched-chainalkyl constituent having from 1 to about 8 carbon atoms, acetyl; vinyl;allyl; hydroxyl; carboxyl; —(CH₂)_(n)—OH, wherein n is an integer in therange of 1 to about 8; —(CH₂)_(n)—COOR₃, wherein n is an integer in therange of 1 to about 8 and R₃ is a member selected from the groupconsisting of any straight- or branched-chain alkyl constituent havingfrom 1 to about 8 carbon atoms, H, or —(CH₂)_(n′), wherein n′ is aninteger in the range of 2 to about 8; and —(CH₂)_(n)—OR₄, wherein n isan integer in the range of 1 to about 8 and R₄ is any straight orbranched-chain alkyl constituent having from 1 to about 8 carbon atoms;and M_(e) is a member selected from the group consisting of Fe, Ti, Ru,Co, Ni, Cr, Zr, Hf, Nb, V and Mo.
 6. The composition according to claim4, wherein M_(e) is selected from the group consisting of Ti, Cr, Cu,Mn, Ag, Zr, Hf and Mo.
 7. The composition according to claim 1, whereinthe metallocene component includes materials within the followingstructure:

wherein R₁ and R₂ occur at least once on each ring, are the same ordifferent and are selected from the group consisting of H; any straight-or branched-chain alkyl constituent having from 1 to about 8 carbonatoms; acetyl; vinyl; allyl; hydroxyl; carboxyl; —(CH₂)_(n)—OH, whereinn is an integer in the range of 1 to about 8; —(CH₂)_(n)—COOR₃, whereinn is an integer in the range of 1 to about 8 and R₃ is a member selectedfrom H; any straight- or branched-chain alkyl constituent having from 1to about 8 carbon atoms; —(CH₂)_(n′), wherein n′ is an integer in therange of 2 to about 8; and —(CH₂)_(n)—OR₄, wherein n is an integer inthe range of 1 to about 8 and R₄ is any straight- or branched-chainalkyl constituent having from 1 to about 8 carbon atoms; Y₁ and Y₂ areoptional and when present at least once are the same or different andare selected from from the group consisting of H, Cl, Br, I, cyano,methoxy, acetyl, hydroxy, nitro, trialkylamines, triaryamines,trialkylphospines, triphenylamine, and tosyl; A and A′ are the same ordifferent and are C or N; m and m′ are the same or different and are 1or 2; and M_(e) is selected from the group consisting of Fe, Ti, Ru, Co,Ni, Cr, Cu, Mn, Pd, Ag, Rh, Pt, Zr, Hf, Nb, V and Mo.
 8. The compositionaccording to claim 7, wherein R₁ and R₂ are each H; Y₁ and Y₂ are eachCl; A and A′ are each N; m and m′ are each 2; and Me is Ru.
 9. Thecomposition according to claim 1, wherein the metallocene component isselected from the group consisting of diaryl phosphino metal-complexedferrocenes, bis-alkyl ferrocenes, and M_(e)[CW₃—CO—CH═C(O⁻)—CW′₃]₂,wherein M_(e) is a member selected from the group consisting of Fe, Ti,Ru, Co, Ni, Cr, Cu, Mn, Pd, Ag, Rh, Pt, Zr, Hf, Nb, V and Mo, and W andW′ are the same or different and are selected from the group consistingof H and halogen.
 10. The composition according to claim 1, wherein themetallocene component is a member selected from the group consisting offerrocenes, titanocenes, and combinations thereof.
 11. The compositionaccording to claim 1, wherein the metallocene component is ferrocene.12. The composition according to claim 1, wherein the photoinitiatorcomponent is selected from the group consisting of 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-2-morpholino propan-1-one, benzophenone,2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1-butanone,2,2-dimethoxy-2-phenyl acetophenone,bis(2,6-dimethoxybenzoyl-2,4,4-trimethyl pentyl)phosphine oxide,2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, bis(2,4,6-trimethylbenzoyl)phenyl phosphine oxide,2-hydroxy-2-methyl-1-phenyl-propan-1-one, alkyl pyruvates, arylpyruvates and combinations thereof.
 13. The composition according toclaim 1, wherein the photoinitiator is a member selected from the groupconsisting of UV photoinitiators, visible light photoinitiators,UV/visible light photoinitiators, and combinations thereof.
 14. Thecomposition according to claim 1, wherein the photoinitiator is a memberselected from the group consiting of dl-camphorquinone,bis(η^(s)-2,4-cyclopentadien-1-yl)-bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl)titanium,and combinations thereof.
 15. The composition according to claim 1,further comprising a member selected from the group consisting ofviscosity-modifying agents, rubber toughening agents, thixotropyrendering agents, thermal stabilizing agents and combinations thereof.16. The composition according to claim 1, wherein the cyanoacrylatemonomer includes ethyl-2-cyanoacrylate which is present in an amountwithin the range of about 97.9% by weight to about 99.4% by weight ofthe total composition, the metallocene component is ferrocene which ispresent in an amount of about 0.1% by weight of the total composition,the photoinitiator component includes the combination ofbis(2,6-dimethoxybenzoyl-2,4,4-trimethyl)pentyl phosphine oxide and2-hydroxy-2-methyl-1-phenyl-propan-1-one which is present in an amountin the range of about 0.5% to about 2% by weight of the totalcomposition, and the sulfur-containing compound is present in an amountin the range of about 0.1% to about 10% by weight of the totalcomposition.
 17. The composition according to claim 1, wherein thecyanoacrylate component includes: ethyl-2-cyanoacrylate which is presentin an amount within the range of about 98.715% to about 98.75% by weightof the total composition and BF₃ in an amount within the range of about0.04% to about 0.075% by weight of the total composition, themetallocene component is ferrocene which is present in an amount ofabout 0.02% by weight of the total composition, the photoinitiatorcomponent includes the combination ofbis(2,6-dimethoxybenzoyl-2,4,4-trimethyl)pentyl phosphine oxide and2-hydroxy-2-methyl-1-phenyl-propan-1-one which is present in an amountof about 1.2% by weight of the total composition, and thesulfur-containing compound is present in an amount in the range of about0.1% to about 10% by weight of the total composition.
 18. Thecomposition according claim 1 in a one-part formulation.
 19. Thecomposition according to claim 18, for use in the manufacture ofarticles using a wicking application.
 20. The composition according toclaim 1, wherein the composition is useful as an adhesive, a sealant ora coating.
 21. The composition according to claim 1, for use in themanufacture of articles having molded polymeric parts to be bondingtogether.
 22. The composition according to claim 1, for use in themanufacture of articles having porous substrates with gaps greater thanabout 0.5 mil therebetween.
 23. The composition according to claim 1,which cures to provide a non-tacky surface in less than 5 seconds.
 24. Amethod of polymerizing a composition, said method comprising the stepsof: (a) providing an amount of the composition according to claim 1: and(b) subjecting the composition to a sufficient amount of saidelectromagnetic radiation to cure the composition.
 25. A reactionproduct formed from the composition according to claim 1, after exposingthe composition to electromagnetic radiation effecting to cure thecomposition.
 26. An article assembled with a composition according toclaim 1, selected from the group consisting of needles, syringes,lancets, hypodermics, injectors, bodily fluid collector sets,cannula/hub assemblies, cannula/tube assemblies, tube sets, intravenoussets, fluid delivery and withdrawal sets, suction tubes, anesthesiamasks, face masks, surgical masks, angioplast catheters, ballooncatheters, disc drives, magnetic sensors, battery holding cartridges,loud speakers, phase holograms, lenses and jewelry, wherein thecomposition is cured by exposure to at least one type of electromagneticradiation selected from the group consisting of ultraviolet light,visible light, electron beam, x-ray and infrared radiation.
 27. A methodof manufacturing an article comprising: selecting portions of needles,syringes, lancets, hypodermics, injectors, bodily fluid collector sets,cannula/hub assemblies, cannula/tube assemblies, tube sets, intravenoussets, fluid delivery and withdrawal sets, suction tubes, anesthesiamasks, face masks, surgical masks, angioplast catheters, ballooncatheters, disc drives, magnetic sensors, battery holding cartridges,loud speakers, phase holograms, lenses or jewelry; applying acomposition according to claim 1 to said portions; and polymerizing saidcomposition to thereby assemble said portions.
 28. A method of repairingan article, comprising: selecting a broken article selected from thegroup consisting of needles, syringes, lancets, hypodermics, injectors,bodily fluid collector sets, cannula/hub assemblies, cannula/tubeassemblies, tube sets, intravenous sets, fluid delivery and withdrawalsets, suction tubes, anesthesia masks, face masks, surgical masks,angioplast catheters, balloon catheters, disc drives, magnetic sensors,battery holding cartridges, loud speakers, phase holograms, lenses andjewelry; applying a composition according to claim 1 to said brokenarticle; and polymerizing said composition to thereby repai said brokenarticle.
 29. A method of using a one-part composition according to claim18 in the assembly of an article which ordinarily would be assembled byapplying onto a substrate a primer, followed by an adhesive composition,comprising: selecting portions of needles, syringes, lancets,hypodermics, injectors, bodily fluid collector sets, cannula/hubassemblies, cannula/tube assemblies, tube sets, intravenous sets, fluiddelivery and withdrawal sets, suction tubes, anesthesia masks, facemasks, surgical masks, angioplast catheters, balloon catheters, discdrives, magnetic sensors, battery holding cartridges, loud speakers,phase holograms, lenses or jewelry; applying a composition according toclaim 1 to said portions; and polymerizing said composition to therebyassemble said portions.